In this work, we establish an indirect amperometric detection method via mounting a single carbon fiber disk working electrode in the end part of a microchannel. This in-channel configuration for microchip capillary electrophoresis brings about that the potential of the working electrode in the case of electrochemical reduction reaction is coupled by the separation electric field, while the potential of the working electrode in the case of electrochemical oxidation reaction is not coupled by the separation electric field. Such a special performance provides a convenient and sensitive approach for indirectly detecting nonelectroactive analytes that relies on amperometric response of dissolved oxygen in solution and directly detecting electroactive analytes based on their own amperometric response on the carbon fiber electrode. This method has shown its essential importance in the analysis of inorganic cations, biomolecules, and electroosmotic flow rates. Based on preliminary results, a detection limit of 1.0 microM for K(+) and Na(+) have been achieved.